Preparation of polychloroacetones



April 1953 c. WOOLF ET AL 2,635,117

PREPARATION OF POLYCHLOROACETONES Filed May 12, 1949 VIIIII/I/IIIIIIII HC/ AND 1 I COOLING mom WATER our g COOLING 9 ix WATER IN ACTIVATED CARBON cHLolaoAclirb/ve C'HLORINE POLYCHLOROACETONE PRODUCT IN V EN TORS.

CYRIL WOOLF EVERETT E. GILBERT ATTORNEY.

Patented Apr. 14, 1953 t I 2;635,11"7 I Q 1 I HREPARATION OF .PQLYCHL'0ROACETON ES -Cyril Woolf, 'L01'1g""-Island City, and Everett "Gilbert; IN eW "York, N. Y.,' assig-nors to Allied Ehemioa'l r&-:Dye iCorporation 'New York, N. 'Y.,

a corporationiof New York v Application'May 12, 1949.,'SeriaLINo.923"?2 :ionims'. (c1. zeo ses) "This "invention "relates to the preparationof of pressure "vesselswhich' are expensive :and diffi- --cult to operate oecaus'e of their susceptibility $0 :attackoy chlorine and H61. I

One object of the invention is tto :preparepoly- :chloroacetones; gAnotheraobject nf the invention .to'produce hexa'chloroacetone "andvpentazchloroacetone :in .high :yields :by chlorination of zatrichloroacetonen A further :aim of the-inven- :tion is to provide processes for the chlorination 10f triohloroacetonestto hexachloroacetoneiin high yields and under economical operating conditions. the gprovision of smoothly operating continuous ichlorination processes {or Fproduction or :such polyohloroacetones. Otherobjects and a'dvan tages 'will appear hereinafter.

accordance with the invention "we found that trichloroacetones ;may :be smoothly and .rapidly rChlQliIlfitBd to polych'loroaoetones'zof fromfi to.6-chlorine;atoms in high yields by Sub,-

' .jecting the =organic :starting material :to action eofechlorine inthe {presence ef/activated carbon as catalyst. The pentachloroacetone and hexachloroacetone products of the invention are of importance as -ohemical intermediates in :jtire graduation of :fluorine deriv.atives,.einsecticides andweed killers, {and have :beenheretofore :difio 3-,.

action. ,However,-we have found that smoother cult to prepare by known methods of chlo-- :rination. v

The figure {of the accompanying drawing is :a cross-sectional view o;f.- -a :reactor which may housed in :carrying out-the processor thertiniparatus'lillustrated, :aitrichloroacetone or isomeric Irnixtiire thereof is"'introdu'ced' throngh "inlet i into-afiverticalreactor l, packed with 'a'ctivawtl :carbcn; inlet being positione'dahoutmidway et another object "of the invention is have downreactor' -side wall "3,-' while introducing chl'o tine through inlet 4 in-"the lower portion of the on mioocnz'oi +5301;

opposite "side -=wall 3 near base 5 of the reaotor. Reaction temperature is maintained :b'el'ow" the boiling point or lthe'iiesireii polychloroac'etone product, 9. -g. 'hexachlor'oacetone, but abovethe "boiling point of the organicreactant, 2i. cartri- -chloroacetone. The liquid polychloroac'etone product fiows downwardly through the reactor countercurrent to the chlorine gas stream and is continuously removed through outlet 5?! posi tioned 'in'base 6 of thereactoroppositechlorine HCl gas formed in the ereac'tion "and residual chlorine pass through p'ipefi .in the top of the reactor and are then "cooled :by passage through reflux condenser '5, "such :gases finally exiting through .outlet :10, of the reflux. condenser. i

A further method ofioarrying-outthe invention involves introduction "of'the iorganic'reactant in the form of a liquid countercurr ently to 501 concurrently with a stream :of gaseous ciflorine in ta vertical reactor packed with activated:oa'r bon andoptionally provided "with a :refiux consdenser. "Reaction temperature is maintained below the boiling spoints of the organic reactant :and :product, ;and the polychloroacetone product is thus collected-in liquid iform. The cameraactor .as shown may be -:employed under-these operating conditions. H

In wall'of the above-noted methods for carrying out the process :of-sthe invention the extent :and velocity of chlorination may "be controlled by variations in reaction temperature, relative-crane .of reactants and rate ofthrqughput thereof.

The organic starting materials in our process are 1,1,3-trichloroacetone or 1 ,l,1-trichloroace- ,tone ormi-xtures thereof. Fllhe organic reactants may ,be introduced into the -reactio n zone =ei-ther the liquidor vapor state.

- .Bestiresultsiin accordance iwithsthe invention lare'obtai-ne'd by using excess chlorine-in the "reand more rapidoperation productive of high yields and lowcby-product formation 15' achieved inaccordance with our'process by employing in the neighborhood of twice the theoretical ichlorine requ'ired. Thus, in-the. chlorination of 1,1,3- trichloroacetone to hexachlomacetoner-inaccordance with itheiequation,

activated ,v Q

:o oocooon+ enal carbon while '3 mols of chlorine are theoretically re ciuired p'ermol of trichloroacetone, we-prerer to employ from "about 5 to *7 molsof chlorine foe'r mol-of tric'hloroaeetone. The chlorine is "usually =maybecome dark in color.

introduced into the bottom of the reactor and flows upwardly either countercurrently to or con currently with the organic reactant.

Any commercial form of activated carbon may be employed as catalyst. The reactor is generally filled to a considerable depth with a bed of such activated carbon particles or powder. However, the activated carbon catalyst particles may be suspended in liquid trichloracetone present in the reaction zone. The amount of catalyst employed may vary widely, sufficient catalyst being utilized to obtain the desired polychlorinated product in good yields commensurate with high rate of throughput of reactants as the particular temperature of reaction. Our experience shows that the activated carbon catalyst has a sufficiently long life to produce as much as 100 times or more its Weight of hexachloroacetone from trichloroacetone. The activated car-. bon should be dried in vacuum before use; otherwise, side reactions increase and the product In starting a run the activated carbon should preferably first be saturated with chlorine and the catalyst bed cooled to room temperature before the organic reactant is commenced to be slowly introduced, after which temperature is brought up to the normal operating value.

In the preparation of the main product of the invention, hexachloroacetone, temperatures of 100-200 C. are ordinarily utilized with temperatures of 140-170 C. and particularly 150-1 60 C. producing most desirable results. In the production. of hexachloroacetone using trichloroacetones as starting material, if reaction temperature is raised beyond 200 C. the amount of high boiling by-product increases.

In commencing operation in accordance with the preferred mode of operation outlined above utilizing'the packed reactor illustrated as applied particularly to production of hexachloroacetone from trichloroacetones, temperature is kept as low as possible, e. g. around 50 C., during initial introduction of trichloroacetones until liquid product begins to flow from the base of the reactor, after which the temperature may be brought up to the normal operating value. This is to allow for dissipation of heatof absorption and reaction until sufficient free liquid is present in the reactor to provide for temperature control by reflux. If desired the temperature of the exothermic reaction may then be regulated by external cooling means or by such methods as use of a large excess-of one of the reactants, e. g. chlorine, or by diluting the reactants with an-inert'gas, e. g. nitrogen. These temperature control expedients may be employed separately or in any combination. It is noted from'the foregoing that reaction temperature may vary so that both'the organic reactant and polychloroacetone product are in liquid form or the organic reactant is in the vapor state and the polychloroacetone product is in the liquid state.

The pressure maintained within the reactor is preferably about atmospheric. The chlorine and organic reactants are under sufficient pressure above that in the reactor to enable these materials to be forced into the reaction zone.

Yields of polychloroacetone product produced in accordance with the invention may range as high as 75-85% of theory based on organic reactant starting material. In the preferred mode of operation for production of liquid hexachloroacetone product from trichloroacetones, yields may be increased by removing any vaporized 4 chloracetones from the exit gases of the chlorination reaction and recycling such chloracetones with new trichloroacetone starting material. Such yields may be further increased by removing and recycling the small amount of pentachloroacetone present in the crude hexachlorocontinuous rate.

acetone product produced. 7

In practice of the preferred embodiments of the invention, the reactor is provided with a reflux condenser for cooling reaction vapors and permitting exit of HCl and excess chlorine from the reactor While returning chloroacetones to the reaction mass. The reactor exit gases are passed through a water scrubber to dissolve HCl and the effluent chlorine may then be dried and recovered.

Materials of construction of the chlorination equipment employed in the instant process include Inconel, Monel metal, stainless steel, glass and silica.

The following detailed examples illustrate the invention, all quantities being expressed in parts by weight:

Example 1.--A reactor vessel is packed with a bed of commercial brand of activated carbon. The reactor is provided with a reflux condenser at the top, a chlorine delivery tube extending; through the bottom of the reactor into the bottom of the catalyst bed, a feed tube for organic reactants extending within the reactor to about the center of the catalyst bed and a syphon at the base of the reactor for continuous removal of liquid product. The reactor is enclosed by a vertical tubular electric furnace through which air may be blown, if necessary, for cooling. Temperatures of reaction are measured within the activated carbon catalyst bed.

During a period of about 40 hours, 2557 parts of a mixture of LLB-trichloroacetone and 1,1,1 trichloroacetone are continuously introduced through the organic reactant feed tube into the center of the catalyst bed while about 6711 parts of chlorine are introduced during this period into the bottom of the catalyst bed at a constant and Temperature of reaction is maintained at 150-160 0. Liquid reaction product flows down the reactor countercurrent to the rising chlorine gas stream and is withdrawn from the bottom of the reactor. Exit gases, after cooling by passage through the reflux condenser to return vaporized chloroacetones to the reaction zone, are scrubbed with water to remove HCl and then conveyed to a chlorine recovery system. 3825 parts of liquid reaction product are recovered consisting of about hexachloroacetone, 4% pentachloroacetone, 8% high boiling byproducts and 3% dissolved chlorine. The yield of hexachloroacetone based on the trichloroacetone starting mixture is about 78%. At the end of the run the catalyst shows no sign of deterioration.

Ezcample 2.-A reactor tower of about 10 cubic feet capacity is packed with activated carbon and provided with temperature recorder, external cooling jacket, reflux condenser, chlorine inlet at the base, organic reactant inlet midway along the tower and exit pipe at the base of the tower for continuous removal of polychloroacetone liquid product.

About 3086 parts of chlorine are fedto the base of the tower at the rate of 129 parts per hour while 1222 parts trichloroacetone are introduced into the middle of the reactor at a rate of 51 parts per hour. The reactants are introduced over a24 hour period, reaction temperature being maintained at 150-160 C. with heat of reaction being removed by cooling. About 1841 parts of crude hexachloroacetone reaction product are continuously removed from the bottom of the tower at a rate of about 77 parts per hour While reactor exit gases, comprising principally HCl and free chlorine, after cooling by passage through the reflux condenser, are scrubbed with water to remove HCl, efiiuent chlorine from the water scrubber being dried and recovered. The crude hexachloroacetone product contains 88% by Weight hexachloroacetone, 4% pentachloroacetone, and 8% high boiling by-products. The yield of hexachloroacetone based on trichloroacetone starting material is about 81% Since various modifications in the invention may be made Without departing from the spirit thereof, the invention is to be taken as limited only by the scope of the appended claims.

We claim:

1. A continuous process of producing hexachloroacetone which comprises introducing a mixture of 1,1,3-trichloroacetone and 1,1,1-trichloroacetone into a reaction zone at a point substantially above the bottom thereof, and introducing excess chlorine into the bottom of said reaction zone, said reaction zone being filled with activated carbon as catalyst at a temperature of 140-1'70 0., and continuously Withdrawing chiefly hexachloroacetone as product from the bottom of said reaction zone.

2. A continuous process of chlorination which comprises introducing a mixture of 1,1,3-trichloroacetone and 1,1,1-trichloroacetone into about the center of a bed of activated carbon as catalyst contained in a reaction zone while introducing from 5 to 7 mols of chlorine per mol of trichloroacetones into the bottom of said catalyst bed, the temperature in said reaction zone being 150160 0., and withdrawing a liquid mixture of hexachloroacetone and pentachloroacetone, predominating in hexachloroacetone, as product from the bottom of said reaction zone.

3. The process of producing a polychloroacetone of from 5 to 6 chlorine atoms which com prises reacting a trichloroacetone with chlorine by introducing said trichloroacetone into a reaction zone at a point substantially above the bottom thereof, said reaction zone being packed with activated carbon as catalyst, and introducing excess chlorine into said reaction zone near the bottom thereof, the temperature of the reaction mixture being -200 C., and withdrawing a polychloroacetone containing from 5 to 6 chlorine atoms as product from a point substantially below the level of introduction of said trichloroacetone into said reaction zone.

4. The process as defined in claim 3 wherein said process is continuous and said product consists chiefly of hexachloroacetone and is continuously Withdrawn from the bottom of said reaction zone.

CYRIL WOOLF. EVERETT E. GILBERT.

References Cited in the file of this patent UNITED STATES PATENTS Number Name Date 2,116,893 Heisel May 10, 1938 2,199,934 Heisel et a1. May 7, 1940 2,375,545 Foster May 8, 1945 FOREIGN PATENTS Number Country Date 638,441 Germany Nov. 16, 1936 OTHER REFERENCES Magidson et al., Chemical Abstracts, vol. 22, pp. 4195-06 (1928).

Groggins, Unit Processes in Organic Synthesis, 3rd Edition, p. 235, copyright 1947 by McGraw-Hill Book Co., New York. 

1. A CONTINUOUS PROCESS OF PRODUCDING HEXACHLOROACETONE WHICH COMPRISES INTRODUCING A MIXTURE OF 1,1,3-TRICHLOROACETONE AND 1,1,1,-TRICHLOROACETONE INTO A REACTION ZONE AT A POINT SUBSTANTAILLY ABOVE THE BOTTOM THEREOF, AND INTRODUCING EXCESS CHLORINE INTO THE BOTTOM OF SAID REACTION ZONE, SAID REACTION ZONE BEING FILLED WITH ACTIVATED CARBON AS CATALYST AT A TEMPERATURE OF 140*-170*C., AND CONTINUOUSLY WITHDRAWING CHEIFLY HEXACHLOROACETONE AS PRODUCT FROM THE BOTTOM OF SAID REACTION ZONE. 